CN105562116A - Preparation method of supported metal catalyst - Google Patents
Preparation method of supported metal catalyst Download PDFInfo
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- CN105562116A CN105562116A CN201510977591.2A CN201510977591A CN105562116A CN 105562116 A CN105562116 A CN 105562116A CN 201510977591 A CN201510977591 A CN 201510977591A CN 105562116 A CN105562116 A CN 105562116A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
Abstract
The invention discloses a preparation method and application of a supported metal catalyst. The supported metal catalyst comprises carrier framework materials and nano particles, loaded on the surfaces of the carrier framework materials, of metal or metal oxide, or metal ions chelated on the surfaces of the carrier framework materials, wherein the metal ions and nano particles of the metal or metal oxide are loaded on the surfaces of the carrier framework materials through the polymerization layers, adhered to the surfaces of the carrier framework materials, of catechol derivatives. The preparation method of the supported metal catalyst has the advantages that the method is simple, various carrier framework materials are used, one or more metal ions or nano particles can be loaded, and universality is achieved; the supported metal catalyst is good in active metal dispersity, large in carrier specific surface area, low in use amount, low in cost, and the like; the catalyst loaded with noble metal is catalyst material which is widely used and environmental friendly and is efficiently applicable to environmental chemical engineering fields such as dye wastewater decoloring, wastewater organic pollutant removing, car tail gas treatment, air purification, hydrogenation and reforming catalytic reaction, gas sensors and fuel cells.
Description
Technical field
The present invention relates to a kind of preparation method that can be used for different carriers area load metallic catalyst, prepared metallic catalyst can be widely used in pollutant removal in environment, dye decolored, the environmental chemical engineering such as vehicle maintenance service, purification of air field.
Background technology
At present, because metal nanoparticle has important application at catalytic field, energy is put into the exploitation of new catalyst by a lot of researcher, and these catalyst relate to the importance that energy environment improvement etc. involves the interests of the state and the people.The key of catalyst effect is the stability of catalyst, i.e. catalyst nanoparticles Long-Time Service stability.As everyone knows, nano particle has high surface energy, in process, easily clustering phenomena occurs, and affects catalyst effect.
Patent CN103934003A(Suzhou Institute of Wuhan University) by silver salt and slaine being prepared under ammonia borane reduction agent effect the catalyst of nucleocapsid structure.Because nucleocapsid structure limits the gathering of silver nano-grain, therefore, the catalyst of preparation has efficient catalytic activity to amino borane hydrolysis.
At purification of air and chemical products catalytic field, load type metal catalyst is an important directions of research at present.As vehicle maintenance service field, the load type gold catalyst that the catalysis process of conventional method grows up have also been obtained suitable application in purifying vehicle exhaust, the metals such as gold and silver platinoid can carry out catalysis to tail gas under the condition that temperature low humidity is high, and effect is fine, the many scientists in the world are just managing the reaction carrying out catalytic car tail-gas with noble metals such as nanometer gold silvers.The stability of nano metal is kept to be the focus studied at present.The golden platinum noble metals high relative to price, silver-colored price is relatively inexpensive, and catalytic performance is more excellent, and therefore the scope of application widely.Carried silver catalyst is applied to ethylene epoxidizing the earliest and prepares oxirane.Nineteen thirty France Lefort catalyst Co. utilizes silver catalyst that direct oxidation of ethylene to is successfully obtained oxirane; Within 1938, UCC company of the U.S. builds up the device of the first in the world cover air direct oxidation ethylene production oxirane according to the achievement in research of Lefort catalyst Co..Nowadays, carried silver catalyst still produces the unique catalyst of ethylene oxide/ethylene glycol.At present, carried silver catalyst is used as the catalyst of oxidation of formaldehyde, ethanol, acetaldehyde, acetone, methyl alcohol, dimethyl ether, propyl alcohol, butanols and propylene etc.
Catechol analog derivative has strong autohemagglutination and adhesive capacity, can adhere to multiple substrate surface, also can form coordinate bond by some metal ion of functional group's chelating such as the copper ion on phenyl ring simultaneously.And gather dopamine composite bed to some metal ion as silver ion, gold ion, platinum ion etc. have stronger reducing power, when surface deposition gathers in the material modified immersion metal salt solution of DOPA amine layer, composite bed energy reducing metal cation generates metal nanoparticle and is deposited on material surface, obtained organic/inorganic composite material.But existing patent is all realize the load of metal nanoparticle at substrate surface by two-step method, first first by catechol analog derivative under the condition of pH>8, oxidation autohemagglutination generates polymer layer, and then be soaked in metal salt solution, and then loaded metal ion or metal nanoparticle.As patent 201010207754.6(mono-kind prepares the method for nano silver-containing anti-bacterial fabric with impregnation technology) by yarn fabric as dopamine modification is carried out on the surfaces such as clothes, then be soaked in liquor argenti nitratis ophthalmicus, obtain the antibiotic fabric of superficial growth silver nano-grain.As patent CN103418250A(method at separation membrane surface in-situ preparation nano particle) be also adopt two-step method by nanometer particle load at separation membrane surface.
In order to simplify the universality of the preparation method of course of reaction and increase substrate loading nanocatalyst, the present invention adopts one-step method to realize at substrate surface loaded metal ion, metal or metal oxide nanoparticles.By catechol derivatives monomer and metal salt solution and base material being directly blended in the aqueous solution, prepare supported catalyst.Wherein metal salt solution plays a part oxidant, promotes the oxidative polymerization of catechol derivatives monomer, and slaine is chelated or is reduced into metal nanoparticle simultaneously.This loading process is simple, is applicable to multiple base material, and reactive adaptation is in the pH of more wide region, does not precipitate as long as meet metal salt solution.
This supported precious metal catalyst is the eco-friendly catalyst material of a class extensive use, can efficient for environmental chemical engineering fields such as decoloring dye waste water, wastewater organic pollutant elimination, vehicle maintenance service, purification of air, hydrogenation and Reforming catalyst reaction, gas sensor, fuel cells.
Summary of the invention
The object of the present invention is to provide a kind of preparation method preparing the substrate loading metallic catalyst of efficient stable.
Second object of the present invention is the application providing a kind of above-mentioned substrate loading metallic catalyst.This catalyst can be applicable to vehicle maintenance service, wastewater treatment, Industrial Catalysis equal energy source environmental chemical engineering field as effective catalyst.
The invention provides following technical scheme:
A metallic catalyst for load, is characterized in that, comprises carrier framework material and load at the described metal of carrier framework material surface or the nano particle of metal oxide, or is sequestered in the metal ion of carrier framework material surface.Described load has the function of catalyst at the metal of carrier framework material surface or metal oxide or metal ion, in dicyandiamide solution still steady load at carrier framework material surface.
Wherein, a kind of preparation method of metallic catalyst of load, is characterized in that, by catechol analog derivative and metal salt solution and described carrier framework material in aqueous blended, after stirring a period of time, obtained by centrifugal or collecting by filtration.
Wherein, carrier framework material, is selected from and has compared with the inorganic material of bigger serface or the particle powder of Inorganic Non-metallic Materials or organic material or sheet material or sheet material.Wherein, inorganic material or Inorganic Non-metallic Materials include but not limited to the (imvite of clay class, tired de-soil, diatomite, bentonite, attapulgite, kaolin, zeolite, illite, galapectite, vermiculite, serpentine etc.), sandstone class (river sand, sea sand, metal sand, sand etc. after natural sandstone efflorescence), stone flour class (medical stone powder, dicalcium powder, talcum powder, dolomite dust, powder of lacquer putty for use on etc.), flyash, flue dust, metal and oxide thereof or hydroxide (aluminium salt, molysite, magnesium salts, silicon salt, titanium salt and complex salt etc. thereof, conventional has aluminium polychloride, PAFC, poly-ferric chloride, polymer phosphate aluminium, polymer aluminium silicate, polymeric aluminium ferrum silicate, calcium aluminate, manganese oxide, iron oxide, aluminium oxide, zirconia, antimony oxide, calcium carbonate, zinc oxide, magnesium hydroxide) etc. one or more.
Wherein, organic material includes but not limited to starch, active carbon, Graphene and Graphene derivative, CNT and derivative, polymer microsphere and powder or diaphragm (as polyethylene, polypropylene, polysulfones, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylamide, polyaniline, polystyrene, cellulose and its derivates).
Wherein, catechol analog derivative, is characterized in that described catechol analog derivative is a kind of organic molecule containing dihydroxy benzenes base section and derivative thereof,
Its general molecular formula is:
Include but not limited to following molecular formula:
Wherein, R1, R2, R3, R4, R5 is identical or different, be selected from independently of one another hydrogen, saturated and undersaturated, straight chain and side chain, replace and unsubstituted C1-10 alkyl, and containing amino, carboxyl, sulfydryl, one or more substituents in halogen, oh group, low-grade alkyl group, lower alkoxy groups, monocyclic aryl, lower acyl groups and their combination; Including, but not limited to DOPA (DOPA), dopamine and salt thereof, 3,4-dihydroxy benzenes methylamines, 3,4-4-dihydroxy benzaldehydes, 3,4-dihydroxy benzenes acetaldehyde, PCA or DOPAC.
Wherein, metal salt solution includes but not limited to one or more in metal sulfate, metal nitrate, metal halide, metal amides, metal carboxylate, metal acetyl acetonate, metal sulfonate, metal phosphate, metal thiocarbamates, metal mercaptide salt, metal carbonate and metal citrate; Described metal comprises lithium, chromium, palladium, copper, aluminium, silver, zinc, manganese, iron, titanium, nickel, cobalt, platinum, lead, manganese, cadmium, mercury, silicon, barium, scandium, vanadium, zirconium, molybdenum, ruthenium, tantalum, tungsten, osmium, iridium and gold.
Wherein, the mass fraction of carrier framework material is 10-99%, is preferably 80%-90%; Slaine mass fraction is 0.1-40.0wt.%, is preferably 1%-20.0wt.%; The mass fraction of catechol analog derivative is 0.01-10.0wt.%, is preferably 1%-10.0wt.%.
Wherein, in reaction system, dicyandiamide solution is buffer solution system, described cushioning liquid to include but not limited in Acetic acid-sodium acetate buffer solution, phosphate buffer, Ning Meng Suan – sodium citrate buffer solution, Lin acid hydrogen Er Na – citrate buffer solution, Lin Ben bis-Jia Suan – hydrochloride buffer, Tris-hydrochloride buffer, boric acid-borate buffer solution and sodium carbonate-bicarbonate buffer solution one or more, choosing of cushioning liquid is relevant to slaine kind used, avoids the generation of slaine or other precipitations in course of reaction; The pH of system is 2-14, is preferably 4-10; Reaction temperature is 10-60 DEG C, is preferably 20-40 DEG C.
Wherein, metallic catalyst is by being embedded into carrier framework material surface with catechol analog derivative chelating or reaction, and wherein catechol analog derivative forms polymer layer in the polymerization of carrier framework material surface.The mass percentage that carrier framework material accounts for described metal catalyst system is 10-99%, is preferably 80%-90%; Metallic catalyst account for described catalyst system mass ratio be 0.1-50.0%, be preferably 1%-20%; The mass ratio that described catechol derivative polymer accounts for described catalyst system is 0.01-50%, is preferably 0.1-10%.
The invention has the beneficial effects as follows:
A kind of preparation method that can be used for the substrate modified metal supported catalyst of catalysis provided by the invention, this catalyst has with low cost, and operation controllability is high, and catalytic effect is more efficient, and catalyst stability can keep the features such as multiple circulations.This supported precious metal catalyst is the eco-friendly catalyst material of a class extensive use, can efficient for environmental chemical engineering fields such as decoloring dye waste water, wastewater organic pollutant elimination, vehicle maintenance service, purification of air, hydrogenation and Reforming catalyst reaction, gas sensor, fuel cells.This new method, still belongs to the first at home and abroad.
Detailed description of the invention
In the present invention, by catechol analog derivative and metal salt solution and described carrier framework material in aqueous blended, stir after 10 minutes-10 hours, obtained by centrifugal or collecting by filtration.
Below by way of specific embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from said method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.Described method is conventional method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Embodiment 1
Be the aqueous solution of 1.0% by configuration concentration soluble in water for 1g imvite, after ultrasonic 2 hours, add the DOPA of 0.125g, after DOPA dissolves completely, add the silver nitrate of argentiferous 0.125g, react 12 hours, eccentric cleaning prepares modified montmorillonoid loaded with nano Argent grain.Wherein, Nano Silver mass ratio is 10.0%, and particle diameter is 5-100nm, and the mass ratio that imvite accounts for montmorillonite loading nano Argent grain is 80.0%.In montmorillonite loading nano Argent grain, the mass ratio of DOPA is 10.0%.
Embodiment 2-6
Be the aqueous solution of 1.0% by configuration concentration soluble in water for 1g imvite, after ultrasonic 2 hours, add 3,4-dihydroxy benzenes methylamines or 3, the 4-4-dihydroxy benzaldehyde or 3 of 0.011g, 4-dihydroxy benzenes acetaldehyde or 3,4-dihydroxy-benzoic acid or DOPAC, add the gold chloride containing golden 0.1g, react 12 hours, eccentric cleaning prepares modified montmorillonoid loaded with nano Argent grain.Wherein, nm of gold mass ratio is 9.0%, and particle diameter is 5-100nm, and the mass ratio that imvite accounts for montmorillonite loading nano gold grain is 90.0%.In montmorillonite loading nano gold grain, the mass ratio of dopamine derivative is 1.0%.
Embodiment 7-13
Be the aqueous solution of 1.0% by configuration concentration soluble in water for 1g imvite, after ultrasonic 2 hours, add 3 of 0.011g, 4-dihydroxy benzenes methylamine or 3, 4-4-dihydroxy benzaldehyde or 3, 4-dihydroxy benzenes acetaldehyde or 3, 4-dihydroxy-benzoic acid or 3, 4-dihydroxyphenyl acetic acid, add Acetic acid-sodium acetate buffer solution or phosphate buffer or citric acid-sodium citrate buffer solution or sodium hydrogen phosphate-citrate buffer solution or phthalic acid-hydrochloride buffer or boric acid-borate buffer solution or sodium carbonate-bicarbonate buffer solution buffer solution adjust ph, add the silver nitrate of argentiferous 0.25g, react 1 hour, eccentric cleaning prepares modified montmorillonoid loaded with nano Argent grain.Wherein, Nano Silver mass ratio is 20%, and particle diameter is 5-100nm, and the mass ratio that imvite accounts for montmorillonite loading nano Argent grain is 79.0%.In montmorillonite loading nano Argent grain, the mass ratio of dopamine is 1%.
Embodiment 14-18
1g polysulfones or polyacrylonitrile or polyvinyl fluoride or polyvinylidene chloride or polyvinylidene fluoride or polyacrylamide film or microballoon are suspended from 3 of 0.011g, in 4-dihydroxy benzenes methylamine water solution, add the silver nitrate of argentiferous 0.25g, react 10 minutes, eccentric cleaning prepares loading type silver catalyst.Wherein, Nano Silver mass ratio is 19.8%, and particle diameter is 5-100nm, and the mass ratio that framework material accounts for catalyst is 79.0%, and the mass ratio of dopamine is 1.2%.
Embodiment 19-24
Added by 1g talcum powder in 3, the 4-dihydroxy benzenes methylamine water solutions of 0.055g, add nickeliferous or cobalt or platinum or lead or manganese or cadmium 0.125g slaine, react 2 hours, eccentric cleaning prepares load type metal catalyst.Wherein, metal quality ratio is 15%, and particle diameter is 5-100nm, and the mass ratio that framework material accounts for catalyst is 80.0%.The mass ratio of dopamine is 5.0%.
It should be noted last that, above detailed description of the invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to example to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (8)
1. the metallic catalyst of a load; it is characterized in that; comprise carrier framework material and load at the described metal of carrier framework material surface or the nano particle of metal oxide or the metal ion being sequestered in described carrier framework material surface; described load has the function of catalyst at the metal of carrier framework material surface or metal oxide or metal ion, and in dicyandiamide solution, steady load is at carrier framework material surface.
2. prepare the preparation method of the metallic catalyst of load described in claim 1 for one kind, it is characterized in that, by catechol analog derivative and metal salt solution and described carrier framework material in aqueous blended, stir after 10 minutes-10 hours, obtained by centrifugal or collecting by filtration.
3. the preparation method of the metallic catalyst of a kind of load according to claim 1 or the catalyst of load according to claim 2, it is characterized in that, described carrier framework material is selected to be had compared with the inorganic material of bigger serface or the particle powder of Inorganic Non-metallic Materials or organic material or sheet material or sheet material, and described inorganic material or Inorganic Non-metallic Materials include but not limited to the (imvite of clay class, tired de-soil, diatomite, bentonite, attapulgite, kaolin, zeolite, illite, galapectite, vermiculite, serpentine etc.), sandstone class (river sand, extra large sand, metal sand, the sand etc. after natural sandstone efflorescence), stone flour class (medical stone powder, dicalcium powder, talcum powder, dolomite dust, powder of lacquer putty for use on etc.), flyash, flue dust, metal and oxide thereof or hydroxide (aluminium salt, molysite, magnesium salts, silicon salt, titanium salt and complex salt etc. thereof, conventional has aluminium polychloride, PAFC, poly-ferric chloride, polymer phosphate aluminium, polymer aluminium silicate, polymeric aluminium ferrum silicate, calcium aluminate, manganese oxide, iron oxide, aluminium oxide, zirconia, antimony oxide, calcium carbonate, zinc oxide, magnesium hydroxide) etc. one or more, wherein organic material includes but not limited to starch, active carbon, Graphene and Graphene derivative, CNT and derivative, polymer microsphere and powder or diaphragm (as polyethylene, polypropylene, polysulfones, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylamide, polyaniline, polystyrene, cellulose and its derivates).
4. the preparation method of the metallic catalyst of load according to claim 2, is characterized in that, described catechol analog derivative is a kind of organic molecule containing dihydroxy benzenes base section and derivative thereof, and its general molecular formula is:
Include but not limited to following molecular formula:
Wherein R1, R2, R3, R4, R5 is identical or different, be selected from hydrogen independently of one another, saturated and undersaturated, straight chain and side chain, replace and unsubstituted C1-10 alkyl, and containing amino, carboxyl, sulfydryl, halogen, oh group, low-grade alkyl group, lower alkoxy groups, monocyclic aryl, one or more substituents in lower acyl groups and their combination, including, but not limited to DOPA (DOPA), dopamine and salt thereof, 3, 4-dihydroxy benzenes methylamine, 3, 4-4-dihydroxy benzaldehyde, 3, 4-dihydroxy benzenes acetaldehyde, 3, 4-dihydroxy-benzoic acid or 3, 4-dihydroxyphenyl acetic acid.
5. the preparation method of the metallic catalyst of load according to claim 2, it is characterized in that, described metal salt solution include but not limited in metal sulfate, metal nitrate, metal halide, metal amides, metal carboxylate, metal acetyl acetonate, metal sulfonate, metal phosphate, metal thiocarbamates, metal mercaptide salt, metal carbonate and metal citrate one or more; Described metal comprises lithium, chromium, palladium, copper, aluminium, silver, zinc, manganese, iron, titanium, nickel, cobalt, platinum, lead, manganese, cadmium, mercury, silicon, barium, scandium, vanadium, zirconium, molybdenum, ruthenium, tantalum, tungsten, osmium, iridium and gold.
6. the preparation method of the metallic catalyst of load according to claim 2, is characterized in that, in reaction system, the mass fraction of described carrier framework material is 10-99%, is preferably 80%-90%; Slaine mass fraction is 0.1-40.0wt.%, is preferably 1%-20.0wt.%; The mass fraction of catechol analog derivative is 0.01-10.0wt.%, is preferably 1%-10.0wt.%.
7. the preparation method of the metallic catalyst of load according to claim 2, it is characterized in that, in described reaction system, dicyandiamide solution is buffer solution system, described cushioning liquid includes but not limited to Acetic acid-sodium acetate buffer solution, phosphate buffer, Ning Meng Suan – sodium citrate buffer solution, sodium hydrogen phosphate-citrate buffer solution, phthalic acid-hydrochloride buffer, Tris-hydrochloride buffer, in boric acid-borate buffer solution and sodium carbonate-bicarbonate buffer solution one or more, choosing of cushioning liquid is relevant to slaine kind used, the generation of slaine or other precipitations is avoided in course of reaction, the pH of system is 1-14, is preferably 4-8, reaction temperature is 10-60 DEG C, is preferably 20-40 DEG C.
8. the preparation method of the metallic catalyst of load according to claim 1 or the catalyst of load according to claim 2, it is characterized in that, metallic catalyst is that wherein catechol analog derivative forms polymer layer in the polymerization of carrier framework material surface by being embedded into metal or the metal oxide nanoparticles of carrier framework material surface with the metal ion or reduction reaction of catechol analog derivative chelating; The mass percentage that described carrier framework material accounts for described metal catalyst system is 10-99%, is preferably 80%-90%; The mass ratio that described metallic catalyst accounts for described catalyst system is 0.1-50.0%, is preferably 1%-20%; The mass ratio that described catechol derivative polymer accounts for described catalyst system is 0.01-50%, is preferably 0.1-10%.
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